EP0170588B1 - Catalyseur et procédé pour le traitement des gaz d'échappement des moteurs à combustion interne - Google Patents

Catalyseur et procédé pour le traitement des gaz d'échappement des moteurs à combustion interne Download PDF

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Publication number
EP0170588B1
EP0170588B1 EP85401489A EP85401489A EP0170588B1 EP 0170588 B1 EP0170588 B1 EP 0170588B1 EP 85401489 A EP85401489 A EP 85401489A EP 85401489 A EP85401489 A EP 85401489A EP 0170588 B1 EP0170588 B1 EP 0170588B1
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EP
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Prior art keywords
catalyst
alumina
catalysts
palladium
rhodium
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EP85401489A
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German (de)
English (en)
French (fr)
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EP0170588A1 (fr
Inventor
Gilbert Blanchard
Michel Prigent
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Pro Catalyse SA
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Pro Catalyse SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals

Definitions

  • the present invention relates to multifunctional catalysts, more particularly intended for the treatment of exhaust gases from internal combustion engines.
  • Multifunctional means catalysts, operating the oxidation in particular of carbon monoxide and of the hydrocarbons present in the exhaust gases as well as the simultaneous reduction in particular of the nitrogen oxides present in these gases.
  • the composition of the exhaust gases can be regulated around a stoichiometric balance such that oxidation and catalytic reduction of its various constituents lead to water, carbon dioxide and nitrogen.
  • the means generally used to adjust the composition of the exhaust gas around this stoichiometry are in particular the continuous adjustment of the air / fuel ratio at the intake of the engine and / or the introduction of additional oxygen upstream of the catalyst. .
  • the composition of exhaust gases thus varies over periods of the order of a second from a composition containing a relative excess of oxidizing compounds (so-called “poor” trimming) to a composition containing an excess of reducing compounds (so-called "trimming”) rich ”) and vice versa.
  • the so-called “lean” setting is such that the amounts of oxygen and nitrogen oxide present are greater than those required to produce the oxidation of the carbon monoxide, hydrocarbons and hydrogen present.
  • the so-called “rich” setting is such that the amounts of carbon monoxide, hydrocarbons and hydrogen present are greater than those required to produce the reduction of the oxygen and nitrogen oxides present.
  • Catalysts have already been proposed for treating such exhaust gases.
  • EP-A-27 069 describes a catalyst comprising a support based on refractory oxide and an active phase consisting of cerium, iron, at least one metal taken from the group comprising platinum and palladium and at least one metal taken from the group comprising iridium and rhodium.
  • multifunctional catalysts which have rhodium, palladium, iron and cerium as their active phase.
  • a multifunctional catalyst for the treatment of exhaust gases from an internal combustion engine, containing a support impregnated with at least one platinum group metal chosen from the group comprising platinum, palladium, ruthenium, rhodium and iridium and at least one base metal chosen from the group comprising in particular cerium, iron, zirconium, cobalt, nickel, zinc, manganese , tungsten.
  • the Applicant has found new multifunctional catalysts based on zirconium, cerium, palladium and rhodium overcoming the drawbacks presented by the catalysts of the prior art and which, completely unexpectedly, prove to have excellent activity as well as '' remarkable stability over time.
  • the present invention in fact relates to a multifunctional catalyst characterized in that it comprises a support on which is deposited by impregnation an active phase consisting of zirconium and cerium and optionally iron, palladium and at least one metal taken from the group comprising iridium and rhodium.
  • the support used according to the invention can in particular be based on refractory oxide in particulate form, the most commonly used being based on alumina.
  • a support is used based on alumina particles preferably having a specific surface of between 25 and 250 m 2 / g and, more particularly between 70 and 150 m 2 / g. It has a total pore volume preferably between 0.5 and 2 cm 3 / g and, more particularly between 0.8 and 1.7 cm 3 / g. It preferably has a macroporosity such that the pore volume of the pores whose diameter is greater than 100 nm is between approximately 0.05 and 0.6 cm 3 / g and, preferably, between 0.2 and 0.5 cm 3 / g.
  • Such supports may in particular have been manufactured from active alumina obtained according to the method described in US-A-2,915,365 and agglomerated according to the method described in US-A-2,881,051.
  • They may also have been manufactured by autoclaving in neutral or acidic medium the preceding agglomerates, drying and calcination in particular as described in FR-A-1 449 904 and FR-A-1 386 384.
  • the alumina supports used may also have been manufactured according to the process described in FR-A-2 399 276.
  • the alumina supports used may also have been manufactured according to the process described in EP-A-15 801.
  • the supports based on alumina particles used according to the invention may have been treated as is well known to those skilled in the art by blowing agents such as those based cellulose, naphthalene, natural gums, synthetic polymers, etc. in order to give them the desired porosity properties.
  • the support used according to the invention can also consist of one or more oxides covering a metallic or ceramic substrate; said substrate preferably being in the form of a structure inert and rigid monolithic type comprising channels or conduits.
  • Such supports are well known to those skilled in the art and have been widely described in the literature, the oxides preferably being used in the form of a film or a coating applied to the substrate.
  • the oxides constituting the coating are most commonly based on aluminum oxide.
  • the metallic substrates used are in particular those obtained from alloys of iron, nickel, chromium, or those obtained from iron, chromium, aluminum and cobalt such as those known under the brand KANTHAL or those obtained from alloys of iron, chromium, aluminum and yttrium and known under the brand FECRALLOY.
  • the metal can also be carbon steel or simple cast iron.
  • pretreat metal substrates based on aluminum by heating in an oxidizing atmosphere under conditions of time and temperature which make it possible to form, from the aluminum contained in the alloy, a surface layer of oxide of aluminum.
  • carbon steels or cast iron they can also be pretreated by annealing iron or steel covered with an aluminum layer to obtain a coating of an aluminum / iron diffusion layer.
  • the substrates of ceramic material used are in particular those comprising as main material cordierite, alumina, mullite, porcelain, boron or silicon carbides.
  • the aluminum oxide coating of these ceramic or metallic substrates can be obtained by application of alumina hydrate and then calcination or by deposition of an aluminum salt and then calcination or by application of a layer of active alumina then calcination.
  • the cell structure can be hexagonal, tetragonal, triangular or wavy, it must allow the passage of gas in the channels or conduits formed during their manufacture by extrusion, rolling, solidification of sheet-shaped elements, etc.
  • the supports used according to the invention are advantageously treated so as to give them good thermal stability over time.
  • the stabilized supports described in FR-A-2 257 335 and FR-A-2 290 950 in the name of Rhône-Poulenc are suitable for the purposes of the invention.
  • the palladium content of the catalyst generally varies between about 0.04 and 3% by weight relative to the finished catalyst and, preferably, between about 0.05 and 0.50% by weight.
  • That of metal from the group consisting of iridium and rhodium generally varies between approximately 0.002 and 0.3% by weight and preferably between approximately 0.005 and 0.1 4t by weight.
  • rhodium associated with palladium it will be preferred to use rhodium associated with palladium.
  • the total content of cerium in the active phase of the catalysts according to the invention is between approximately 0.1 and approximately 10% by weight relative to the finished catalyst. This content is preferably between 0.3 and 5.0%.
  • the zirconium content of the active phase of the catalysts according to the invention is between approximately 0.1 and approximately 10% by weight relative to the finished catalyst. This content is preferably between 0.1 and 6%.
  • the catalysts can also comprise at least one of the following metals iron, tungsten, nickel, manganese, tin, germanium, cobalt, uranium, rhenium. The total content by weight of these metals added to the support is between approximately 0.2 and 5%.
  • the catalysts according to the invention can be prepared according to current methods, preferably by impregnation of the support by means of a solution of mineral or organic compounds of the metals which it is desired to introduce.
  • the impregnation can be done using solutions common to metals or successively with different solutions.
  • the support is successively impregnated with a solution containing compounds of cerium, zirconium and optionally of iron, then with one or more solutions containing compounds of palladium and rhodium which it is desired to introduce.
  • cerium, zirconium and iron which can be used, there may be mentioned in particular the salts of cerium, zirconium and iron and more particularly cerous nitrate, cerous acetate, cerous chloride, nitrate ammonium ceric, zirconyl nitrate, zirconium tetrachloride, ferric nitrate, ammoniacal iron nitrate and ferric chloride.
  • rhodium of palladium which can be used, mention may in particular be made of hydrated rhodium trichloride, palladium chloride, palladium nitrate as well as rhodium III chloropentamine dichloride and palladium dichloride Tetramine.
  • the impregnation depth can be advantageously adjusted by the use of methods known to those skilled in the art and in particular by adding a certain amount of mineral or organic acid to the solution of precious metals.
  • Nitric, hydrochloric and hydrofluoric acids or acetic, citric, oxalic acids are commonly used.
  • the catalyst is then dried and then activated in an air stream at a temperature between about 300 and 800 ° C for a few hours.
  • a support consisting in particular of an alumina coating deposited on a metallic or ceramic substrate
  • it is advantageously carried out by bringing the substrate into contact with an aqueous dispersion of an alumina precursor which contains in addition salts or oxides of cerium, zirconium and possibly of iron, one dries then one calcines at 300 - 700 ° C approximately, one repeats these operations possibly, then introduced the precious metals and one terminates the operations in the way which has been explained above in the case of supports based on refractory oxide particles.
  • the catalysts according to the invention make it possible to very effectively remove most of the carbon monoxide, unburnt hydrocarbons as well as nitrogen oxides present in the exhaust gases of internal combustion engines and that , moreover, they have remarkable stability over time.
  • a binder and an alumina filler are prepared according to the process described in EP-A-73 703.
  • Part of this powder is calcined in air at 600 ° C for 2 hours to obtain the charge of alumina (1).
  • alumina binder (I) 200 g are dispersed in the form of a powder in 2000 cm 3 of distilled water, the mixture is stirred for 10 minutes and then 800 g of alumina load (I) are added, the mixture is further stirred for 10 minutes.
  • the viscosity of the suspension obtained is 25 centipoise.
  • This suspension is used for coating a 1.98 liter ceramic monolith structure sold by the company CORNING, presenting 400 cells by Square Inch, the 1.98 liter monolith is immersed in the suspension at pH: 3.4 containing 30% by weight of alumina.
  • the aforementioned support is drained and dried so that the channels are emptied, then it is calcined at 600 ° C for 3 hours.
  • the monolith thus coated is immersed in an aqueous solution of cerium nitrate for 30 minutes, then it is drained and dried at 150 ° C. and calcined at 700 ° C. for 3 hours.
  • the concentration of cerium nitrate in the solution is such that, after immersion and calcination, the monolith contains 8.0% by weight of cerium.
  • the substrate is then impregnated by soaking in an aqueous solution of palladium nitrate and hydrated rhodium trichloride.
  • the concentrations of palladium nitrate and rhodium trichloride are such that the monolith is impregnated with 2.0 g of palladium and 0.10 g of rhodium. After 30 minutes of contact, the monolith is dried at 150 ° C and then activated at 500 ° C for 3 hours in a calcination oven.
  • the catalyst (A) thus prepared contains, by weight relative to the monolithic catalyst, 0.200% of palladium, 0.10% of rhodium and 8% of cerium.
  • An alumina binder (II) is prepared according to the method described in EP-A-15 801.
  • An alumina gel cake is produced by continuous precipitation of a sodium aluminate solution with a nitric acid solution.
  • the salt cake is drained, filtered, washed and then treated at 115 ° C for 24 hours in a stirred autoclave.
  • the product obtained is in the form of a paste containing 12% of alumina counted in A1 2 0 3 .
  • the photograph of this product obtained with an electron microscope shows that it consists of ultra-fine, entirely fibrillar boehmite composed of single crystals of dimension 50 to 100 nm.
  • the paste containing 12% alumina is spray-dried at 250 ° C in order to form it alumina binder powder.
  • An alumina (II) charge is prepared as follows: 900 g of alumina beads of gamma structure prepared according to the methods described in FR-A-1 449 904 and FR-A-1 386 364 are prepared by autoclaving in the presence of acid from active alumina agglomerates, drying and calcination. These alumina beads obtained have a specific surface of 100 m 2 / g, a total pore volume of 0.90 cm 3 / g and a volume of 0.40 cm 3 / g consisting of macropores having a diameter greater than 100 gm. These beads are impregnated with 800 cm 3 of an aqueous solution of ferric nitrate containing 70 g of iron.
  • the beads After 30 minutes of contact, the beads are dried at 150 ° C and then calcined in air at 700 ° C for 3 hours.
  • This suspension is used for coating a 1.2 liter metallic monolith structure made from a metal sheet known under the brand name FECRALLOY.
  • the substrate is then impregnated by soaking in an aqueous solution of palladium nitrate and hydrated rhodium trichloride, the concentrations of which are such that the monolith is impregnated with 3.0 g of palladium and 0.3 g of rhodium.
  • the catalyst (B) thus prepared contains, by weight relative to the monolithic catalyst, 0.200% of palladium, 0.020% of rhodium, 3.5% of iron impregnated on the coating of alumina.
  • 100 g of alumina beads are prepared according to the method described in FR-A-2 449 474.
  • These beads have a specific surface of 100 m 2 / g, a total pore volume of 1.20 cm 3 / g and a volume of 0.45 cm 3 / g constituted by macropores having a diameter greater than 100 nm.
  • the beads After 30 minutes of contact, the beads are dried at 150 ° C and then calcined in air at 700 ° C for 3 hours.
  • the beads After 30 minutes of contact, the beads are dried at 150 ° C and then calcined at 500 ° C for 3 hours in a stream of air flowing at 200 liters per hour.
  • the catalyst (C) thus prepared contains, by weight relative to the support, 0.200% of platinum, 0.010% of rhodium, 2.0% of cerium, 3.5% of zirconium and 1% of iron.
  • An alumina suspension is prepared as described in Example 1.
  • This suspension is used for coating a ceramic structure as in Example 1.
  • the monolith coated as in Example 1 is immersed in an aqueous solution of cerium nitrate and zirconium nitrate, the concentrations of which are such that, after immersion and calcination, the monolith contains 2.5% by weight of cerium and 5, 5% by weight of zirconium.
  • the substrate is then impregnated and calcined as in Example 1.
  • the catalyst (D) thus prepared contains by weight relative to the monolithic catalyst 0.20% of palladium, 0.010% of rhodium, 2.5% of cerium and 5.5% of zirconium.
  • An alumina binder (II) is prepared as described in Example 2.
  • An alumina filler (III) is prepared as described in Example 2 by impregnating 300 g of alumina beads per 800 cm 3 of an aqueous solution of ferric nitrate, cerous nitrate and zirconyl nitrate containing 30 g of iron, 70 g of cerium and 70 g of zirconium.
  • a 1.2 liter metallic monolith structure is coated with the suspension of alumina binder (I) and of alumina filler (III) as described in Example 2.
  • the substrate is then impregnated and calcined as in Example 2.
  • the catalyst (E) thus prepared contains, by weight relative to the monolithic catalyst, 0.200% of palladium, 0.020% of rhodium, 1.5% of iron, 3.5% of cerium and 3.5% of zirconium impregnated on the coating of alumina.
  • alumina beads 100 g are impregnated as described in Example 3 with an aqueous solution of cerous nitrate, zirconyl nitrate and ferric nitrate containing 2.0 g of cerium, 3.5 g of zirconium and 1 .0 g of iron.
  • the beads are dried at 150 ° C and then calcined in air at 750 ° C for 3 hours.
  • the beads After 30 minutes of contact, the beads are dried at 150 ° C and then activated at 500 ° C for 3 hours in a stream of air flowing at 200 liters per hour.
  • the catalyst (F) thus prepared contains by weight relative to the support: 0.320% of palladium, 0.016% of rhodium, 2.0% of cerium, 3.5% of zirconium and 1.0% of iron.
  • the present example resembles the results obtained for the chemisorption of carbon monoxide with the various catalysts (A), (B), (C), (D), (E) and (F) described respectively in Examples 1, 2, 3,4, 5 and 6.
  • the procedure used consists in bringing the catalysts under sweeping of a mixture composed of 90% nitrogen and 10% water at 850 ° C. for 100 hours. This procedure is used to simulate the sintering of the metallic phase of the catalysts tested in endurance or engine test for 600 hours when the aging cycle includes a 10-minute plateau at 850 ° C per one-hour cycle as described in example 8.
  • the amount of carbon monoxide chemisorbed by the catalysts prepared according to the invention is, in all cases greater than that of the catalysts prepared according to the prior art, which means that the accessibility of the palladium particles in the catalysts according to the invention, calcined at high temperature is, in all cases, greater than the accessibility of the particles of palladium or platinum in the catalysts of the prior art aged under the same conditions.
  • EXAMPLE 8 ENDURANCE RESISTANCE OF CATALYSTS A, B, C, D, E and F FOR THE SIMULTANEOUS REMOVAL OF CARBON MONOXIDE, HYDROCARBONS AND NITROGEN OXIDES IN THE EXHAUST GASES OF AN ENGINE OPERATING ON THE Wealth 1 on a test strip
  • the engine used for these tests is a Renault 18 USA type engine with a displacement of 1647 cm 3 fitted with a fuel injection supply of the BOSCH L-JETRONIC brand, regulated at richness 1 thanks to an oxygen sensor placed in exhaust manifold outlet
  • the fuel consumed by the engine in these tests is unleaded petrol, however containing a residual lead content adjusted in all cases to 0.013 g / liter.
  • the performances of the catalysts are determined after 35 minutes of stabilization in the second phase at 475 ⁇ 10 ° C.
  • an experimental catalytic converter of the radial circulation type with a volume of 1700 cm 3 produced according to the principle described in FR-A-2 270 444 was adapted on the exhaust line to a distance of about 1.20 m from the engine.
  • the monolith catalysts were mounted in welded metal casings and installed on the exhaust line at a distance of about 0.80 m from the engine.
  • the elimination rate of each of the three pollutants is measured periodically at 475 ⁇ 10 ° C by analyzing the gases upstream and downstream of the pots.
  • Table 1 below collates the results obtained at the start of the test and after 600 hours of walking.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
EP85401489A 1984-07-30 1985-07-19 Catalyseur et procédé pour le traitement des gaz d'échappement des moteurs à combustion interne Expired EP0170588B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8412047 1984-07-30
FR8412047A FR2568143B1 (fr) 1984-07-30 1984-07-30 Catalyseur et procede pour le traitement des gaz d'echappement des moteurs a combustion interne

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EP0170588A1 EP0170588A1 (fr) 1986-02-05
EP0170588B1 true EP0170588B1 (fr) 1988-06-29

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EP85401489A Expired EP0170588B1 (fr) 1984-07-30 1985-07-19 Catalyseur et procédé pour le traitement des gaz d'échappement des moteurs à combustion interne

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US (1) US4680282A (enrdf_load_stackoverflow)
EP (1) EP0170588B1 (enrdf_load_stackoverflow)
JP (1) JPS6193832A (enrdf_load_stackoverflow)
KR (1) KR920005084B1 (enrdf_load_stackoverflow)
DE (1) DE3563514D1 (enrdf_load_stackoverflow)
FR (1) FR2568143B1 (enrdf_load_stackoverflow)

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DE3563514D1 (en) 1988-08-04
FR2568143B1 (fr) 1986-12-05
JPS6193832A (ja) 1986-05-12
FR2568143A1 (fr) 1986-01-31
US4680282A (en) 1987-07-14
EP0170588A1 (fr) 1986-02-05
KR860000890A (ko) 1986-02-20
JPH0480738B2 (enrdf_load_stackoverflow) 1992-12-21
KR920005084B1 (ko) 1992-06-26

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